JPH09194565A - Cyclic carbonate resin composition and its cured product - Google Patents
Cyclic carbonate resin composition and its cured productInfo
- Publication number
- JPH09194565A JPH09194565A JP1039696A JP1039696A JPH09194565A JP H09194565 A JPH09194565 A JP H09194565A JP 1039696 A JP1039696 A JP 1039696A JP 1039696 A JP1039696 A JP 1039696A JP H09194565 A JPH09194565 A JP H09194565A
- Authority
- JP
- Japan
- Prior art keywords
- cyclic carbonate
- resin composition
- epoxy resin
- amine
- opening polymerization
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明における環状カーボナ
ート樹脂組成物は、重合時に体積膨張を示し、寸法精度
や密着性等が要求される成形材料、複合材料、注型材
料、封止材料、塗料および接着剤等の原料として有用で
ある。TECHNICAL FIELD The cyclic carbonate resin composition according to the present invention shows a volume expansion during polymerization and is required to have dimensional accuracy, adhesiveness, etc., molding materials, composite materials, casting materials, sealing materials, paints and coating materials. It is useful as a raw material for adhesives and the like.
【０００２】[0002]
【従来の技術】エポキシ樹脂は、硬化する際、体積収縮
を発生する。これら収縮は、硬化物の物性に大きな影響
を及ぼし、ボイド、クラック、外観不良等の発生あるい
は接着強度の低下等種々の問題を引き起こすため、注型
材料、封止材料、接着材料等の分野で大きな問題となっ
ている。もし、重合時に非収縮性を示す材料が出来れ
ば、寸法精度の向上やそり、歪み、剥離発生の低減によ
る精密な成形、内部応力の低減による材料強度や接着力
の向上等が期待できる。上記、問題を解決するため、例
えば、シリカ、炭酸カルシウム、アルミナ等の無機充填
剤を添加し、硬化収縮の低減を図っている。しかしなが
ら、こうのような無機充填剤の添加では、強度の向上に
効果がある反面、樹脂組成物の粘度が上昇するため、作
業性が悪い等の問題がある。また、エポキシ樹脂と相溶
性のある樹脂をエポキシ樹脂に添加し、これによって体
積収縮を防ぐ試みも行われている（特公昭５８−５７４
２３公報）が、硬化物の物性低下、特に耐熱性の低下を
招くことが多いので好ましくない。また、環状カーボナ
ート化合物は、開環重合時に体積が増大する現象が報告
され、前記の各種用途への応用が注目されている。例え
ばトリフルオロメタンスルホン酸メチルや三フッ化ホウ
素エーテル錯体等のルイス酸系カチオン重合開始剤およ
びナトリウムメトキシド等のアルコキサイド系やｎ−ブ
チルリチウム、ｓｅｃ−ブチルリチウム等のアルキルリ
チウム系をアニオン重合開始剤として開環重合し、体積
膨張を示すことが知られている（マクロモレキュールズ
(Macromolecules),Vol.24,No.15,4229-4235(1991)、日
本化学会第６５春季年会講演予稿集２７１項（１９９３
年）、第４３回高分子学会年次大会予稿集２９４項（１
９９４年））。BACKGROUND OF THE INVENTION Epoxy resins undergo volumetric shrinkage when cured. These shrinkages have a large effect on the physical properties of the cured product, and cause various problems such as the occurrence of voids, cracks, poor appearance, etc., or a decrease in adhesive strength.Therefore, in the fields of casting materials, sealing materials, adhesive materials, etc. It is a big problem. If a material exhibiting non-shrinkage during polymerization can be obtained, improvement in dimensional accuracy, precise molding by reducing warpage, distortion, and peeling, and improvement in material strength and adhesion by reducing internal stress can be expected. In order to solve the above problems, for example, inorganic fillers such as silica, calcium carbonate, and alumina are added to reduce the curing shrinkage. However, addition of such an inorganic filler has an effect of improving the strength, but on the other hand, there is a problem that the workability is poor because the viscosity of the resin composition increases. In addition, an attempt has been made to prevent the volume shrinkage by adding a resin compatible with the epoxy resin to the epoxy resin (Japanese Patent Publication No. 58-574).
23) is not preferable because it often causes deterioration of the physical properties of the cured product, especially heat resistance. Further, it has been reported that the cyclic carbonate compound increases in volume during ring-opening polymerization, and attention has been paid to its application to the above various uses. For example, a Lewis acid-based cationic polymerization initiator such as methyl trifluoromethanesulfonate or boron trifluoride ether complex, an alkoxide-based initiator such as sodium methoxide, or an alkyllithium-based initiator such as n-butyllithium or sec-butyllithium is anionic polymerization initiator. It is known to undergo ring-opening polymerization and show volume expansion (Macromolecules
(Macromolecules), Vol.24, No.15, 4229-4235 (1991), Proceedings of the 65th Spring Annual Meeting of the Chemical Society of Japan, Item 271 (1993).
), Proc. Of the 43rd Annual Meeting of the Polymer Society of Japan, Section 294 (1)
994)).
【０００３】ルイス酸系カチオン重合開始剤を用いた環
状カーボナート化合物の開環重合は、トリフルオロメタ
ンスルホン酸メチルや三フッ化ホウ素エーテル錯体等の
強酸であるルイス酸を用いるため重合時の取り扱いが困
難であり、また、水分による影響が大きいため作業性が
悪かった。さらに、酸成分が存在するため金属が腐食す
る等の問題が生じ、電子材料用としては用いることがで
きなかった。また、ナトリウムメトキシド等のアルコキ
サイド系やｎ−ブチルリチウム、ｓｅｃ−ブチルリチウ
ム等のアルキルリチウム系開始剤を用いるアニオン重合
による環状カーボナート化合物の開環重合法は、水分に
より開始剤の活性が低下し、開環重合への影響が著しく
大きい、またナトリウムイオン、リチウムイオン等のイ
オン性不純物が存在するため、電子材料用としては用い
ることが出来ず、工業的に有用な用途が見出されるに至
っていなかった。さらに、環状カーボナートとエポキシ
ドとの共重合は試みられているが、カチオン重合の反応
（第４２回高分子討論会予稿集２１３９頁（１９９３
年）では水分の影響を受けやすく、また、配位アニオン
重合触媒を用いた反応では触媒の作製が多段階になると
共に金属塩の残留物が残り、いずれも工業的には用いら
れていない（Polymer,Vol.33,No.9,1941-1948(1992))。Ring-opening polymerization of a cyclic carbonate compound using a Lewis acid type cationic polymerization initiator is difficult to handle at the time of polymerization since Lewis acid which is a strong acid such as methyl trifluoromethanesulfonate and boron trifluoride ether complex is used. Moreover, the workability was poor because the influence of water was great. Furthermore, the presence of an acid component causes problems such as corrosion of the metal, and cannot be used for electronic materials. In addition, the ring-opening polymerization method of a cyclic carbonate compound by anionic polymerization using an alkoxide-based initiator such as sodium methoxide or an alkyllithium-based initiator such as n-butyllithium or sec-butyllithium reduces the activity of the initiator due to moisture. , Has a great influence on ring-opening polymerization, and cannot be used for electronic materials because of the presence of ionic impurities such as sodium ion and lithium ion, and industrially useful applications have been found. There wasn't. Furthermore, although the copolymerization of cyclic carbonate and epoxide has been attempted, the reaction of cationic polymerization (Proceedings of the 42nd Symposium on Polymers, 2139 (1993)
Year) is susceptible to moisture, and the reaction using a coordinated anionic polymerization catalyst requires multiple steps of catalyst preparation and leaves a metal salt residue, which are not industrially used ( Polymer, Vol.33, No.9, 1941-1948 (1992)).
【０００４】[0004]
【発明が解決しようとする課題】本発明の目的は、硬化
時に体積膨張する化合物を工業的に有用な開始剤を用い
てエポキシ樹脂と共重合することにより、硬化前後での
収縮を抑制し、密着性、熱的に優れた樹脂を提供するも
のである。The object of the present invention is to suppress shrinkage before and after curing by copolymerizing a compound that expands in volume during curing with an epoxy resin using an industrially useful initiator, It is intended to provide a resin excellent in adhesion and heat.
【０００５】[0005]
【課題を解決するための手段】本発明者らは上記問題を
解決するために、環状カーボナート化合物とエポキシ樹
脂とを共重合させる検討を行った結果、下記で示される
環状カーボナート化合物とエポキシ樹脂がアミン系アニ
オン重合開始剤により工業的に容易に開環重合し、該樹
脂組成物が、硬化前後で低収縮を示し、密着性、熱的に
優れることを見出し本発明を完成するに至った。Means for Solving the Problems In order to solve the above problems, the present inventors have conducted a study to copolymerize a cyclic carbonate compound and an epoxy resin, and as a result, the cyclic carbonate compound and the epoxy resin shown below have been identified. The present invention has completed the present invention by finding that the ring-opening polymerization is industrially easily performed with an amine-based anionic polymerization initiator, and that the resin composition exhibits low shrinkage before and after curing, and is excellent in adhesiveness and heat.
【０００６】即ち、本発明は、一般式（１）又は一般式
（２）で示される環状カーボナート化合物とエポキシ樹
脂とアミン系アニオン開環重合開始剤を成分として用い
ることを特徴とする環状カーボナート化合物であり、That is, the present invention uses a cyclic carbonate compound represented by the general formula (1) or general formula (2), an epoxy resin, and an amine-based anionic ring-opening polymerization initiator as components. And
【化１】 （式中、ｘ、ｙは、０から３までの整数、Ｒ1、Ｒ2 は１
５以下の炭素数を含むアルキル基、フェニル、ナフチル
等の芳香族基、又はアリル基を示す）Embedded image (In the formula, x and y are integers from 0 to 3, and R 1 and R 2 are 1
Indicates an alkyl group containing 5 or less carbon atoms, an aromatic group such as phenyl or naphthyl, or an allyl group)
【化２】 （式中、ｘ、ｙは、０から３までの整数、Ｒ3、Ｒ4 は環
状化合物を示す） また、環状カーボナート化合物とエポキシ樹脂との重量
比が１／９９〜８０／２０の範囲である前記の樹脂組成
物であり、また、該樹脂組成物を硬化させてなる硬化物
である。Embedded image (In the formula, x and y are integers from 0 to 3, and R 3 and R 4 are cyclic compounds.) Further, the weight ratio of the cyclic carbonate compound and the epoxy resin is in the range of 1/99 to 80/20. It is a certain resin composition described above, or a cured product obtained by curing the resin composition.
【０００７】本発明における環状カーボナート化合物の
好ましい例として次の化合物が挙げられる。Preferred examples of the cyclic carbonate compound in the present invention include the following compounds.
【化３】 Embedded image
【０００８】なお、本発明における環状カーボナート化
合物は一種の化合物だけでなく、二種以上の化合物の混
合物として用いてもよい。環状カーボナート化合物の製
造方法は、公知の方法（第３９回高分子学会年次大会予
稿集２８４頁（１９９０年））によって得られたもの使
用することができる。The cyclic carbonate compound in the present invention may be used not only as one compound but also as a mixture of two or more compounds. The cyclic carbonate compound can be produced by a known method (the 39th Annual Meeting of the Polymer Society of Japan, Proceedings 284 (1990)).
【０００９】上記反応に使用されるエポキシ樹脂として
は、エポキシ樹脂であれば特に限定されないが、ビスフ
ェノール系エポキシ樹脂、フェノールノボラック型エポ
キシ樹脂、クレゾールノボラック型エポキシ樹脂等の芳
香族型エポキシ樹脂、脂環型エポキシ樹脂、複素環型エ
ポキシ樹脂等が好ましいとして挙げられ、単独又は２種
以上の化合物の混合物としてもちいてもよい。The epoxy resin used in the above reaction is not particularly limited as long as it is an epoxy resin, but it is an aromatic epoxy resin such as bisphenol epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, or alicyclic. -Type epoxy resin, heterocyclic epoxy resin and the like are mentioned as preferable examples, and they may be used alone or as a mixture of two or more compounds.
【００１０】本発明で用いられるアミン系開環重合開始
剤としては、ジエチレントリアミン、トリエチレンテト
ラミン、テトラエチレンペンタミン、ジエチルアミノプ
ロピルアミン、ベンジルジメチルアミン、２−（ジメチ
ルアミノメチル）フェノール、２,４,６−トリス（ジア
ミノメチル）フェノール、トリエチルアミン、ジエチル
アミン、エチルアミン、アニリン、テトラメチルグアニ
ジン、アルキルｔｅｒｔモノアミン等が挙げられる。特
に、アミン系開環重合開始剤が環状アミン化合物である
開始剤としては、２−メチルイミダゾール、２−エチル
−４−メチルイミダゾール、２−ウンデシルイミダゾー
ル、２−ヘプタデシルイミダゾール、２−フェニルイミ
ダゾール、１−ベンジル−２−メチルイミダゾール、１
−シアノエチル−２−メチルイミダゾール、２,４−ジ
アミノ−６−[２−メチルイミダゾリル−(１)]−エチル
Ｓ−トリアジン、ピペリジン、Ｎ,Ｎ’−ジメチルピペ
ラジン、ピリジン、ピコリン 等が挙げられる。The amine ring-opening polymerization initiator used in the present invention includes diethylenetriamine, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, 2,4, 6-tris (diaminomethyl) phenol, triethylamine, diethylamine, ethylamine, aniline, tetramethylguanidine, alkyl tert-monoamine and the like can be mentioned. In particular, as the initiator in which the amine ring-opening polymerization initiator is a cyclic amine compound, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole are used. , 1-benzyl-2-methylimidazole, 1
-Cyanoethyl-2-methylimidazole, 2,4-diamino-6- [2-methylimidazolyl- (1)]-ethyl S-triazine, piperidine, N, N'-dimethylpiperazine, pyridine, picoline and the like.
【００１１】環状アミン化合物中、特に、１,８−ジア
ザビシクロ[５,４,０]ウンデク−７−エン（ＤＢＵ）、
トリエチレンジアミン、４−ジメチルアミノピリジンは
一般式（１）および一般式（２）で示される環状カーボ
ナート化合物との反応が著しく速く、また分子量、収率
が高い。Among the cyclic amine compounds, 1,8-diazabicyclo [5,4,0] undec-7-ene (DBU),
The reaction of triethylenediamine and 4-dimethylaminopyridine with the cyclic carbonate compounds represented by the general formulas (1) and (2) is extremely fast, and the molecular weight and the yield are high.
【００１２】前記のアミン系アニオン開始剤は、一般式
（１）および一般式（２）で示される環状カーボナート
化合物に対して、０.０１〜１５重量％、好ましくは、
０.１〜５重量％の範囲内で用いられる。０.０１重量％
未満では、重合は進行するものの、長時間を必要とする
ため好ましくない。一方、１０重量％を超える濃度で
は、低分子量体が生じ易くなるため好ましくない。環状
カーボナート化合物とエポキシ樹脂の成分の割合は、環
状カーボナート化合物とエポキシ樹脂との重量比が、１
／９９〜８０／２０、好ましくは、５／９５〜６０／４
０である。１／９９未満では、硬化後の収縮は、エポキ
シ樹脂単独の反応よりも抑制されるが、密着性が低くな
り、低収縮の効果が低い。一方、８０／２０を越えると
体積膨張は大きくなるが、硬化物が作製できず好ましく
ない。これら重合反応の条件は、硬化促進剤の種類、量
により異なるが、通常、室温〜２００℃、好ましくは、
５０〜１８０℃の範囲である。The above-mentioned amine anion initiator is 0.01 to 15% by weight, preferably 0.01 to 15% by weight, based on the cyclic carbonate compound represented by the general formula (1) or (2).
It is used within the range of 0.1 to 5% by weight. 0.01% by weight
If it is less than 1, the polymerization will proceed, but it requires a long time, which is not preferable. On the other hand, if the concentration exceeds 10% by weight, a low molecular weight compound is easily generated, which is not preferable. The ratio of the components of the cyclic carbonate compound and the epoxy resin is such that the weight ratio of the cyclic carbonate compound and the epoxy resin is 1
/ 99 to 80/20, preferably 5/95 to 60/4
0. When it is less than 1/99, the shrinkage after curing is suppressed more than the reaction of the epoxy resin alone, but the adhesiveness is low and the effect of low shrinkage is low. On the other hand, when it exceeds 80/20, the volume expansion becomes large, but a cured product cannot be produced, which is not preferable. The conditions of these polymerization reactions vary depending on the type and amount of the curing accelerator, but are usually room temperature to 200 ° C., preferably
It is in the range of 50 to 180 ° C.
【００１３】本発明の樹脂組成物は、必要に応じて、充
填材、染料、顔料等の添加剤を配合することができる。
充填材としては、木粉、パルプ粉、各種織物粉砕物、熱
硬化樹脂積層板および成形品の粉砕物等の有機質のも
の、シリカ、ガラス、タルク、アルミナ、炭酸カルシウ
ム、カーボン等の無機粉末、ガラス繊維、カーボン繊
維、マイカ等の無機繊維等を選ぶことができる。The resin composition of the present invention may contain additives such as fillers, dyes and pigments, if necessary.
Examples of the filler include organic powders such as wood powder, pulp powder, various crushed textiles, crushed thermosetting resin laminates and molded products, and inorganic powders such as silica, glass, talc, alumina, calcium carbonate, and carbon; Inorganic fibers such as glass fiber, carbon fiber, and mica can be selected.
【００１４】[0014]
【実施例】以下、実施例および比較例に基づいて、本発
明を具体的に説明する。密度は、（株）柴山科学器械製
作所社製密度勾配管法比重測定装置Ａ型で臭化カリウ
ム、または、臭化カルシウム水溶液２５℃中で測定し
た。The present invention will be specifically described below based on examples and comparative examples. The density was measured with a density gradient tube method specific gravity measuring device A type manufactured by Shibayama Scientific Instruments Co., Ltd. in an aqueous potassium bromide or calcium bromide solution at 25 ° C.
【００１５】［実施例１］環状カーボナート、ＹＸ−４
０００Ｈ、及び、ＤＢＵを表１に示す組成比（重量部）
で配合し、混合して樹脂組成物を調整した。得られた樹
脂組成物について２５℃における比重を測定する一方、
この樹脂組成物を１１０℃２時間、１５０℃８時間でそ
れぞれ加熱硬化し、硬化前後における比重差から体積膨
張率を求めた。また、ＴＭＡ（熱機械的試験）にて熱膨
張係数ならびにガラス転移温度を測定した。引張りせん
断強さは積層板金メッキ面に上記、混合した樹脂をコー
ティングし、その上にチップを付着させ、１１０℃２時
間、１５０℃８時間加熱し、ＡＩＫＯＨエンジニアリン
グ（株）社製シーピーユーゲージを用いて測定を行っ
た。結果を表１に示す。Example 1 Cyclic Carbonate, YX-4
Composition ratio (parts by weight) of 000H and DBU shown in Table 1
Was blended and mixed to prepare a resin composition. While measuring the specific gravity at 25 ° C. of the obtained resin composition,
This resin composition was heated and cured at 110 ° C. for 2 hours and 150 ° C. for 8 hours, and the volume expansion coefficient was determined from the difference in specific gravity before and after curing. Further, the thermal expansion coefficient and the glass transition temperature were measured by TMA (thermo-mechanical test). The tensile shear strength is obtained by coating the above-mentioned mixed resin on the surface of the laminated sheet metal plating, adhering chips onto it, heating at 110 ° C. for 2 hours and 150 ° C. for 8 hours, and using AI KOH Engineering Co., Ltd. Was measured. The results are shown in Table 1.
【００１６】[0016]
【表１】 [Table 1]
【００１７】（実施例２〜７、比較例１〜５）表１及び
表２に示す割合で各材料を混合した後、実施例１と同様
にして各種物性を測定した。なお、比較例１、２、５の
ガラス転移温度はＤＳＣにて測定した。測定結果を表１
及び表２に示す。(Examples 2 to 7, Comparative Examples 1 to 5) After mixing the respective materials at the ratios shown in Tables 1 and 2, various physical properties were measured in the same manner as in Example 1. The glass transition temperatures of Comparative Examples 1, 2, and 5 were measured by DSC. Table 1 shows the measurement results
And Table 2.
【００１８】[0018]
【表２】 [Table 2]
【００１９】[0019]
【発明の効果】環状カーボナートとエポキシ樹脂をアミ
ン系アニオン開環重合開始剤を用いて反応することによ
り硬化収縮の少ない重合物が得られ、密着性、熱的に優
れた性質を示す。従って、注型材料、封止材料、接着材
料等の工業材料の用途に有用である。EFFECTS OF THE INVENTION By reacting a cyclic carbonate with an epoxy resin using an amine-based anionic ring-opening polymerization initiator, a polymer having a small curing shrinkage can be obtained and exhibits excellent adhesion and thermal properties. Therefore, it is useful for applications of industrial materials such as casting materials, sealing materials, and adhesive materials.
フロントページの続き (51)Int.Cl.6 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０８Ｇ 64/02 ＮＰＴ Ｃ０８Ｇ 64/02 ＮＰＴ Ｃ０８Ｋ 5/10 ＮＫＺ Ｃ０８Ｋ 5/10 ＮＫＺ 5/16 ＮＬＢ 5/16 ＮＬＢ Ｃ０８Ｌ 63/00 ＮＨＸ Ｃ０８Ｌ 63/00 ＮＨＸ Continuation of the front page (51) Int.Cl. 6 Identification code Internal reference number FI Technical display location C08G 64/02 NPT C08G 64/02 NPT C08K 5/10 NKZ C08K 5/10 NKZ 5/16 NLB 5/16 NLB C08L 63/00 NHX C08L 63/00 NHX
Claims (3)
る環状カーボナート化合物とエポキシ樹脂とアミン系ア
ニオン開環重合開始剤を成分として用いることを特徴と
する環状カーボナート樹脂組成物。 【化１】 （式中、ｘ、ｙは、０から３までの整数、Ｒ1、Ｒ2 は１
５以下の炭素数を含むアルキル基、フェニル、ナフチル
等の芳香族基、又はアリル基を示す） 【化２】 （式中、ｘ、ｙは、０から３までの整数、Ｒ3、Ｒ4 は環
状化合物を示す）1. A cyclic carbonate resin composition comprising a cyclic carbonate compound represented by the general formula (1) or (2), an epoxy resin, and an amine-based anionic ring-opening polymerization initiator as components. Embedded image (In the formula, x and y are integers from 0 to 3, and R 1 and R 2 are 1
Indicates an alkyl group containing 5 or less carbon atoms, an aromatic group such as phenyl or naphthyl, or an allyl group) (In the formula, x and y are integers from 0 to 3, and R 3 and R 4 are cyclic compounds.)
との重量比が１／９９〜８０／２０の範囲である請求項
１記載の樹脂組成物。2. The resin composition according to claim 1, wherein the weight ratio of the cyclic carbonate compound and the epoxy resin is in the range of 1/99 to 80/20.
なる硬化物。3. A cured product obtained by curing the resin composition according to claim 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1039696A JPH09194565A (en) | 1996-01-24 | 1996-01-24 | Cyclic carbonate resin composition and its cured product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1039696A JPH09194565A (en) | 1996-01-24 | 1996-01-24 | Cyclic carbonate resin composition and its cured product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09194565A true JPH09194565A (en) | 1997-07-29 |
Family
ID=11748978
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1039696A Pending JPH09194565A (en) | 1996-01-24 | 1996-01-24 | Cyclic carbonate resin composition and its cured product |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09194565A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6730772B2 (en) * | 2001-06-22 | 2004-05-04 | Venkatram P. Shastri | Degradable polymers from derivatized ring-opened epoxides |
| US6800663B2 (en) | 2002-10-18 | 2004-10-05 | Alkermes Controlled Therapeutics Inc. Ii, | Crosslinked hydrogel copolymers |
| JP2009537684A (en) * | 2006-05-22 | 2009-10-29 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン | Low shrinkage epoxy-cation curable composition |
| CN102838960A (en) * | 2012-08-29 | 2012-12-26 | 江苏博特新材料有限公司 | Low-viscosity epoxy structure adhesive and preparation method thereof |
| JP2013213187A (en) * | 2011-12-21 | 2013-10-17 | Toyo Ink Sc Holdings Co Ltd | Photopolymerizable oxirane-based resin composition, photopolymerizable coating agent, photopolymerizable adhesive agent, and optical film laminate body |
| WO2015180656A1 (en) * | 2014-05-28 | 2015-12-03 | 苏州大学张家港工业技术研究院 | Carbonate polymer with disulfur five-membered ring functional group on side chain and application thereof |
| WO2023008351A1 (en) * | 2021-07-26 | 2023-02-02 | 味の素株式会社 | Transparent resin composition |
-
1996
- 1996-01-24 JP JP1039696A patent/JPH09194565A/en active Pending
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6730772B2 (en) * | 2001-06-22 | 2004-05-04 | Venkatram P. Shastri | Degradable polymers from derivatized ring-opened epoxides |
| US6800663B2 (en) | 2002-10-18 | 2004-10-05 | Alkermes Controlled Therapeutics Inc. Ii, | Crosslinked hydrogel copolymers |
| JP2009537684A (en) * | 2006-05-22 | 2009-10-29 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェン | Low shrinkage epoxy-cation curable composition |
| JP2013213187A (en) * | 2011-12-21 | 2013-10-17 | Toyo Ink Sc Holdings Co Ltd | Photopolymerizable oxirane-based resin composition, photopolymerizable coating agent, photopolymerizable adhesive agent, and optical film laminate body |
| CN102838960A (en) * | 2012-08-29 | 2012-12-26 | 江苏博特新材料有限公司 | Low-viscosity epoxy structure adhesive and preparation method thereof |
| WO2015180656A1 (en) * | 2014-05-28 | 2015-12-03 | 苏州大学张家港工业技术研究院 | Carbonate polymer with disulfur five-membered ring functional group on side chain and application thereof |
| KR20170012424A (en) * | 2014-05-28 | 2017-02-02 | 브라이트제네 바이오-메디컬 테크놀로지 코., 엘티디. | Carbonate polymer with disulfur five-membered ring functional group on side chain and application thereof |
| US10072122B2 (en) | 2014-05-28 | 2018-09-11 | Brightgene Bio-medical Technology (Suzhou) Co., Ltd. | Carbonate polymer containing a functional group of disulfide five-membered ring in the side chain and application thereof |
| WO2023008351A1 (en) * | 2021-07-26 | 2023-02-02 | 味の素株式会社 | Transparent resin composition |
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